Journal of Environmental Radioactivity 192 (2018) 342–348

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Journal of Environmental Radioactivity

journal homepage: www.elsevier.com/locate/jenvrad

Alpha emitter NORM crystal scales in industrial pipelines: A study case T

a b b a,∗ b
H. Barros , M. Diaz-Lagos , S.A. Martinez-Ovalle , L. Sajo-Bohus , J.L. Estupiñan
a
Universidad Simón Bolívar, Caracas, Venezuela
b
Universidad Pedagógica y Tecnológica de Colombia, Tunja-Boyacá, Colombia

A R T I C LE I N FO A B S T R A C T

Keywords: Radioactive related pollution due to suspended particulate matter dispersion is an important workplace and
NORM health care issue. Recycling oil production ducts and contaminated production equipment, represent a health
Scales hazard to workers and public alike. Radioactive plate-out NORM scales with crystal deposit is analyzed by
Alpha emitters different techniques; results provide proper information on physico-chemical features and emitted alpha par-
Nuclear track detector
ticles. Recommendations for handling and recycling procedures are included in relation to health risk and
radiological hazard.

1. Introduction
The first Venezuelan oilfield of importance, Mene Grande, was
discovered by Caribbean Petroleum (15 April 1914). After a century,
the current production rate rose to around 1.6 Mbd and currently is one
of the main supports of the national economy. As early as 1954, in the
USA, reports on radioactivity levels in crude petroleum were already
available with concentrations above the average soil value (i.e. > 40
Bq·kg−1). Contrastingly, in a review made by (Smith, 1992), radium
concentrations in produced waters were reported as high as 2 × 104 Bq.
kg−1, while oil production tubes shows inlays mainly as concentrated
inorganic solids such as barite (BaSO4) and also strontium and calcium
sulphate, with maximum Ra concentrations of 5,88 × 106 Bq. kg−1.
The scale formation including crystals by chemical reactions, hinder
the extraction of the crude in the production line. The deposited matter,
with time becomes a great obstacle since reduce the fluid flow trans-
versal section with a velocity that depends on changes in temperature,
pressure, release of gas and pH of the production water while trans-
ported to the surface along with the crude oil. Deposited substances are
related directly to transported fluid, often rich in naturally occurring
radioactive matter (NORM) such as water dissolved radium salts as ions
(Ra+2). The latter has a chemical similarity to barium, strontium or
calcium, and during precipitation processes involving the mentioned
alkaline earth elements, the 228,226Ra is involved, causing accumulation
of e. g. radium and its daughter's radon, polonium and bismuth iso-
topes. Some minerals from the geological formation of the deposits such
as aragonite, dolomite, limestone, quartz, alkali feldspar as well as clay
presence, have been observed in the scales (Matta et al., 2002). Com-
pounds formed (precipitated) in the tubes are bound to the scale matrix
and during crude extraction it can be mixed with suspended matter
transported from the petroleum deposit.
In Venezuela, discarded clogged pipes pose a problem to the in-
dustry since these after a given operation time (spanning from months
to a few years) are stored at a considerable cost in open areas. There
stored pipes are awaiting a recycling process in order to recover the
metal for further use. It has been reported that NORM contamination, at
the mentioned storage sites, may induce a non-negligible dose rate to
workers during handling (Zwack et al., 2013), mostly related to the Ra
isotopes and its daughters (including radon gas) that may pose an en-
vironmental burden.
One of the main challenges in the recycling process, is the removal
of radioactive rich compounds scales attached to tubes, valves and
other equipments, due to barite and calcite insolubility in water (EPA/
625/R-96/010). Nevertheless, remedial actions are at hand and in fact,
some authors (Attallah et al., 2012, 2013) have reported that surfac-
tants solutions could be effectively employed for pipe cleaning; how-
ever, the development of an effective solution to reduce polluting
wastes is still under study. High concentration (Matta et al., 2002)
scale, if exposed to the environment, is subject to dispersion by wind or
flooding with the risk of inhalation or entering the water way. An im-
mediate consequence is that radioactivity levels near the storing site
will be modified with deep effects on human habitat (Heaton and
Lambley, 1995). Specific literature deals with this kind of environ-
mental problems and Basic Safety Standards Directive (Mundigl, 2014)
should be considered in remedial action programs.
For the first time and up to our knowledge, this is the first report
concerning measurements of radioactive oil-production related scales
from Venezuela pipe storage sites. Results of the analysis of samples

∗
Corresponding author.
E-mail address: lsajo@usb.ve (L. Sajo-Bohus).

https://doi.org/10.1016/j.jenvrad.2018.07.008
Received 28 June 2018; Accepted 9 July 2018
0265-931X/ © 2018 Elsevier Ltd. All rights reserved.
H. Barros et al.
taken from PDVSA storage sites, will complement basic technical in-
formation. The main objective is to contribute to establish convenient
cleaning and recycling procedures in an integral frame of NORM/
TENORM management program. Further the aim is to attend the radi-
ological protection principles and avoid/reduce radiation exposures so
to minimize health hazards and environmental pollution.
2. Materials and methods
The selection of inlay sampling was based on an extensive field
survey that covered different storing sites along the country. Those that
shown dose rates up to 25 μSv/h determined using portable GM
monitors (Teletektor and Ludlum Model 5) were selected for this study.
Samples were collected, carefully removing matter from discarded pipe
inner walls and labeled accordingly considering also radiation level.
Due to the anoxic (depleted of dissolved oxygen) chemical environment
that features hydrocarbon deposits, a very low content of U and Th is
expected in the waters that make scales (Al Masri, 2006; Kpeglo et al.,
2016). Radioactive families are found in low concentration in fine grain
mineral fractions that are dragged from the deep underground Vene-
zuelan crude oil deposits. As mentioned, most frequently found radio-
nuclide in scales are 226, 228Ra and progenies, carried by produced
waters where these exhibit a relatively high concentration (alpha
counting rate). On the field, measurements with a ZnS(Ag) alpha par-
ticle detector (Alpha Scintillator Model 43-5 coupled to the Ludlum
Model 12 Survey Meter) confirmed the accurrence of alpha emitters (10
Bq. g−1). Afore mentioned samples must be considered as TENORM
since the external radiation rate go beyond 0.5 μSv/h, (1 mSv.a−1). In
fact, surveyed scale exceed by far the referenced value. It is worth to
mention that due to the low penetration of alpha particles in dense
matter such as crystal minerals (e. g. barite has 4.2–4.47 g/cm3 and
Aeff = 31), the nuclear track methodology or NTM, offer the possibility
observe from track diameter distribution the surface layer thickness
variation (some micrometers) that cover barite individual crystals.
These could be covered up to half a millimeter or more, well above the
10 μm range of alpha particles with 4 MeV in barite, (Fujiwara et al.,
2016).
From the collected two dozen samples it was possible to recognize
four groups by visual appearance of the surficial matter and dose rate
values. At the laboratory, the undisturbed original scale samples were
analyzed by different equipment i. e. JEOL USA Scanning Electron
Microscopes, X-Ray Fluorescence (XRF) and X-ray diffraction.
In order to assess the alpha emitter's surface concentration and
distribution along the scales, the NTM was chosen, for its versatility and
robustness, relatively of low cost and because it can be implemented in
industrial areas where the detector installation does not require spe-
cialized personnel. The applied methodology is related to etched nu-
clear track digitalized image analysis. This technique has been suc-
cessfully used in the past and its response to alpha particles showed its
usefulness for environmental dosimetry, (Sajo-Bohus et al., 1997).
3. Results and observations
The four set of samples underwent analysis with equipment avail-
able at the two Institutions in the frame of an international collabora-
tion. Fig. 1 shows the superficial aspect of the different scale samples;
these are related to sample obtained after grinding them softly in a
wooden mortar, so to preserve the mineral shapes and size fraction
distribution. Their dose rate values for 200 g samples in containers of
8 cm diameter were measured, all of them in close contact with
counting device. Their mineralogical characterization was made by
optical microscopy and in Fig. 1 we report for few samples the surficial
appearance.
For the sample A it can be seen that small crystals are mixed mainly
with the densest asphaltenic fractions found in crude oil. That is why
this sample look like black sandpaper, with average thicknesses around
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Journal of Environmental Radioactivity 192 (2018) 342–348
one mm. Crystals are translucent (internally they are clean or pure),
with straight shape borders which shows the usual orthorhombic
structure of barite. Crystal habit is tabular parallel to base and massive,
which is consistent with the structure of this inorganic salt. Individual
crystal sizes vary from tiny fractions up to 500 μm or more. The main
composition of the crystalline minerals is barite (BaSO4) as confirmed
by XRD and SEM. It is remarkable that in the given sample it was not
observed any other mineral (up to the equipment detection limit or
LLD). The sample A is the most radioactive of the set, with dose rate
several times higher in comparison to others currently under study.
Sample B has the appearance of iron oxide ex-foliations, with
thickness below 2.5 mm and does not seem to retain crude oil. The scale
that was facing the tube is brown colour and has almost a regular shape,
and in contrast, the side facing the fluid flux (crude and water) shows
an irregular porous surface. However the crushed minerals, under an
optic microscope, look similar to those of sample A. In fact, it was later
confirmed by SEM that many of them are barite, but with more irre-
gular crystal borders, nevertheless still with a massive crystal habit. The
sample contains several other grain minerals, mainly associated to iron,
from the oxidation of the internal tube face. Mineral size distribution is
similar to sample A with dose rate several times lower. It can be due to
two main factors: lower content of barite crystals or lower content of
radium in the barite crystals.
The sample C has practically the same appearance of sample B, si-
milar to iron oxide without oil and with lower porosity and with
thickness less than one mm. Under the microscope, it appears like a
mixed set of minerals, where the barite crystals are smaller in size in
comparison with the two previous samples A and B. It was later con-
firmed the presence of quartz and iron oxides. Individual barite crystals
are smaller in comparison to sample B, and do not exceed 100 μm.
General size fraction of the different minerals is featured by smaller
crystals than in sample B, this will be better shown later. The sample C,
is slightly less radioactive than sample B, as can be inferred from the
dose rates.
Sample D is thick, white in colour and belongs to a completely
different type of incrustations (inlays). Sediment would seem like ce-
ment or calcium carbonate with a relatively soft surface. Under an
optical microscope it can be noted the absence of grain crystals, while
only mineral amorphous conglomerates appear and are mainly calcite
with negligible radioactivity (dose rate is comparable to background
radiation level).
Although the definition of mineral is referred only to natural com-
pounds, and knowing that the compounds produced during industrial
process must be called mineralloids, nevertheless we will refer to them
as minerals as well, based on their main compositional and structural
features. In Fig. 2, it is shown the scanning electron microscope (SEM,
JEOL JSM-3690) images of the set of samples from A to D with am-
plification ×100 and ×1000 (×750 for D).
Samples were sifted with a 150 μm sieve in order to avoid the
presence of larger crystals or conglomerated matter.
In all pictures given in Fig. 2, barite appears as bright surfaces,
justified by backscattered electron having a higher yield for compounds
with high atomic number such as Ba. Sample A shows only barite
crystals, which can be sub-micron in size. All the X-Ray elemental
analyses performed to different individual grains in sample A show a
mass relation 4:1 for the Ba to S ratio confirming the exclusive presence
of barite. Sample B also presents barite as its main mineral composition
and contains more grains with sizes below 10 μm. Sample C has lower
content of barite crystals with size around 50 μm and several smaller
fractions; other crystals can be spotted as well e.g. quartz. We may
observe 3 distinct samples types or classes (A, B and C). Note that small
barite grain fractions can be generated by the perturbation of the
samples, for its relatively low hardness (between 3 and 3.5 Mohs). Since
the ionic radius of barium (136 pm for Ba+2) is relatively close to that
of radium (152 pm for Ra+2), in general terms, there exists a relation
between the barium concentration and the presence of radium in
H. Barros et al. Journal of Environmental Radioactivity 192 (2018) 342–348

Fig. 1. General appearance of the radioactive scales. (top (T): pictures frame 1 cm), and their minerals after grinding (bottom (B): pictures frame 1 mm). AT and AB:
Barite and crude, dose rate 24 μSv/h. BT and BB: Barite and iron oxide, dose rate 6 μSv/h. CT and CB: Barite, quartz and iron oxide, dose rate 3 μSv/h. DT and DB:
Calcite, dose rate comparable to the background value.

production waters (Al Masri, 2006) and in oil pipe scales (Attallah
et al., 2012). It is also worthy to mention that Venezuelan crude sulphur
content is one of the highest worldwide, ranging up to 6% in the studied
areas, participating in chemical reactions during the oil/water extrac-
tion process. Besides, barite (BaSO4) is chemically inert and insoluble
(solubility in water is just 2–3 mg. L−1), so if scale radioactive materials
are dispersed, the grains will prevail and dispersion/dilution by lix-
iviation will not occur. The barite environmental concentrations in
small grain fractions, increases the probability of inhalation and in-
gestion of radioactive minerals transported e.g. by wind, implying a
radiological risk related to internal body exposure (contamination).
The sample D shows a typical structure of calcite powder, shape;
size fractions call attention more to a grinding process due to the cal-
cite's low hardness value (number 3 on the Mohs hardness scale by
definition); observation that justifies its only occurrence.
Results of the elemental analysis for the inlay samples are reported
in Table 1. They were determined scanning at least 10 image frames
(×100) using the SEM electron XRF micro probe, the average variation
of the reported measurements (sigma) ranges from 3 to 10%.
X-Ray diffraction results given in Fig. 3, provide further indication
on the presence of crystalline compounds such as barite in sample A,
barite, iron oxide and by lower percentage, quartz in samples B and C,

Fig. 2. Backscattering electron microscopy images of the scale samples. A: Barite and crude. B: Barite and iron oxide. C: Barite, SiO2, Fe oxide. D: Calcite.

344
H. Barros et al. Journal of Environmental Radioactivity 192 (2018) 342–348

Table 1 Table 2
Main minerals and elemental analysis of the oil tube's scale samples. Sample A radiation count rate for different size fractions.
Sample XRD C O Al Si S Ca Fe Sr Ba Particle size Weight by Count rate Count rate Count rate
[min−1] [min−1] [min−1]
A BaSO4 36 8 – – 11 – – 1 45
B BaSO4 + SiO1 – 27 – 6 10 9 12 – 37 [μm] [%] α+β+γ γ (and β) mainly α
C BaSO4 + SiO2 – 58 4 5 4 2 14 – 14
D CaCO3 8 61 – – – 27 3 – – > 600 9 200 150 50
< 600 63 710 530 180
< 150 28 490 360 130

Fig. 3. X-Ray difractograms of scale types A: BaSO4 (barite) and D: CaCO3
(calcite).
and calcite in sample D.
The diffractograms were obtained from an X-ray equipment, AXS
BRUKER D8 Advance with copper anode (30 mA 40 kV), scanning angle
from 10 to 70°, step size 0.02°, scanning time in every step was 0.07 s.
In sample A the carbon is associated to the oil crude fraction, and
traces of strontium are also observed (interpreted as SrSO4). Samples A
and B shows barite and quartz, the iron oxide is also recognized,
however it must be an amorphous formation of oxide, since there is no
evidence of its crystal structure in the X-ray difractogram. On the other
hand, those two samples also have some percentage of calcium; prob-
ably in form of calcium carbonate, but its relative low concentration,
make it difficult to identify it on the difractogram. Sample C exhibits
also some aluminum, i. e. aluminum-silicates associated to particles
dragged from the formation, similar to the case of the quartz. Sample D
analysis shows calcite with some iron oxide. The inlays formation of
different minerals are related to geochemistry of the geological deposit
and to the hydrochemistry of the produced waters, since the latter in-
duce mineral association in different degrees.
Sample C dose rate value is comparable to background with the
other sample with NORM content are related to U and Th concentration
in minerals. Their decay product, such as Ra daughters, enter the
mainstream fluid during production by lixiviation process and de-
pending on geological strata i.e. porosity, grain size, mineral types and
water geochemistry, reach the surface. In the particular case of the
scales with calcite (ionic radius of 100 pm), Ca hinders Radium nu-
cleation on the crystalline structure of CaCO3. This is justified by the
larger Ra+2 ionic radius, more than one and a half times in comparison
to Ca+2
The most radioactive sample of the set, is A; after mechanical dis-
aggregation it was sieved and separated in three grain size fractions, for
further analysis as indicated in Table 2.
After that each fraction was weighted, counting rates were mea-
sured in identical conditions using a GM monitor; that has a thin Be
window (that provided counting for alpha, beta and gamma radiation).
A Pb collimator with 1 cm2 window was employed. In order to assess
the contribution of alpha particles, the measurements were performed
in two modes: by measuring directly over the sample surface (1 cm
above) and interposing a fine aluminum paper sheet to absorb alpha
particle. Note that a 0.1 mm Al foil stops all the impinging alphas, since
the highest energy from the Ra decay chains, is the 8785 keV emitted by
the 212Po; its penetration range in Al is just 0.05 mm. However, all the
beta particles having energy higher than 125 keV pass through Al foil,
others charged particle will be absorbed. During this experiment, beta
particle intensity is attenuated and high energy beta electrons are
counted by gamma photons. A reduction of 25% was attained when
covered by 0.1 mm thick aluminum foil, which absorbed the emitted
alpha particles. Since in the attenuated experiment only gammas and
betas with higher energies (> 125 keV) are measured, then the corre-
sponding counting rate must be related to the barite crystal whole vo-
lume, independently of their grain size. Fig. 4, shows counting rates
plotted vs. the % of mass of the different grain fractions.
The linear correlation between the GM counting rate (mainly
gammas and fast betas) with the mass for different grain fractions im-
plies that these provide the same radiation by unit of mass, which is in
concordance with the assumption of a homogeneous Ra distribution
along the different crystal sizes (note that on Fig. 4 the 119 cpm in-
tercept corresponds to background). The justification is given by
Fig. 4. GM counting rate vs. mass % for different grain fractions. Data from
Table 2.

345
H. Barros et al.
Fig. 5. Scale sample covered by a PADC (CR-39™) alpha particle detector
(2 × 2 cm2).
nucleation process of the barite onto the inner tube wall, due to Ba and
Ra homogeneous occurrence in solution. These elements precipitate
along the pipes in a relatively long section up to several meter as
measured in stored tubes. Since these did come from the same pro-
duction well in is deduced that the relation between Ba and Ra should
be stoichiometric in each case.
The A sample was also studied using PADC detectors. A relatively
plane unperturbed piece of this sample was chosen and a CR-39™ nu-
clear track detector was carefully placed on the top of the sample sur-
face and left for a given irradiation time (see Fig. 5). After exposure and
etching in a 6 N, NaOH solution at 70° in water bath for 6 h, was washed
in distilled water, dried and then analyzed by a light transmission mi-
croscope (Leica, model DM 750/10 × 0.22) (Espinosa, 1994). This unit
is coupled to a light transmission CCD camera to produce digitalized
images from that, track density is determined (Nejad et al., 2014).
Nuclear etched track densities are reported as observed through a
sequence of digitalized photomicrograph (Fig. 6). The field view for
each picture is 1.31 × 0.98 mm2 and 135 field views were employed to
determine track density.
The track density is 225 ± 4% in an area of 1.28 mm2, equivalent
to 165 tracks per mm2. Then the estimated specific alpha flux emitted
from the surface is 27.5 mBq.mm−2; considering a solid angle of 2° and
PADC detector efficiency of 10−3. Since both radium chains, 226, 228Ra,
basically emit 5 alpha particles per Bq, the previous surface flux implies
a total Ra surface concentration of 5.5 mBq.mm−2, this measurement
takes into account only the Ra which produce alpha particles that
Fig. 6. Nuclear track sizes evidence low number of elliptic shapes induced by alpha particles impinging at an angle above the critical value.
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Journal of Environmental Radioactivity 192 (2018) 342–348
escape from the barite crystals. The hill like map evidences a rather
non-uniform alpha counting track density. That is imputable to several
causes. Firstly, the alpha particles come only from the barite mineral,
few or none originate from areas covered by crude oil. Even assuming
crude oil covered barite crystal, only a negligible number of alpha
particles will have enough kinetic energy (above the threshold energy
Eth > 200 MeV) that will induce a visible track. In that case its diameter
values will change depending on the oil deposit layer in opposition of
the observed result in Fig. 6. Contour map (Fig. 7) shows gradients in
the radioactive scale surface; this map only reflects alpha particles
coming from a very thin layer of each crystal.
Numbers in Fig. 7 indicate track density along the contours; higher
values are in the range of 280-250 tracks per unit area and a lower
range is 70–110 tracks. Asphaltenes in-situ are typically stable, believed
to be held in solution by resins (similar in structure and chemistry, but
smaller in size). During crude oil production flowing material destabi-
lize and precipitate under changes in temperature (to a lesser extent),
by pressure and chemical reactions. Inlay deposition velocity and re-
sulting thickness depend on both precipitation and flow shearing.
Worth to mention that sample A look like asphaltene deposit with barite
crystals. In this context, assuming an average density of 1.2 g cm−3 and
alpha particles (4,66 - 8,79 MeV) the asphaltene thickness measured by
alpha track, is around 0.03–0.07 mm.
4. Radiation risk considerations
To provide a better understanding of consequences for workers in
the cleaning of clogged pipes rich in NORM and thereby improving
decision-making for a safety recycling procedure, some consideration
on the involved risk factors should be mentioned. The approach is to
consider the working environment describing the risk factors belonging
to the two main categories, external and internal radiation risk factors.
In spite of the external gamma dose, the more important aspect related
to handling TENORM contaminated oil pipes is the inhalation (or in-
gestion) of fine size particles with high activity concentration of alpha
emitter radioisotopes. The hazard ramifications and heath evaluation of
this aspect requires the radioactivity concentration values, and the size
and mass fraction of the suspended particle matter in air, at working
environment, and finally the exposure time or the total intake dose.
Regarding the size of the air transported particles, usually it is assumed
H. Barros et al.
as the fractions smaller than 5 μm, in absence of specific aerodynamic
studies (ICRP Publication 66, 1994). On the other hand, the activity
concentrations reference level used to consider a given material as a
NORM is 10 Bq. g−1 of radium (228Ra + 226Ra), following the IAEA
recommended limit (IAEA, 2017). If the actual concentrations are
above this value, then the material has to be considered as NORM,
consequently it must be characterized and handled properly.
The oil industry in Venezuela is of such a magnitude that requires a
proper resource administration with reliable methods, economically
feasible and a methodology as simple as possible to follow. In this
context, the spectrometric techniques are expensive if compared to
NTM, so this last can be employed conveniently as a screening method
to provide a first radiometric characterization as well as a technique to
select only the samples of interest for a more detailed study. It is a well
established method and the related technology is easier to implement in
industrial environments when compared to alpha or gamma spectro-
metry. Additionally, it is pertinent to highlight the fact that nuclear
track detectors are adequate to assess the surface Ra concentration of
barium sulphate crystals, and may help to evaluate gradient con-
centration.
Observing Fig. 2, minerals associated to radium and alpha particle
emitters, can be found in small size fractions, even well below 10 μm,
that poses a radiological health risk in cases of inhalation. The nasal
cavity, trachea and lung retain increasingly smaller size particles that
suggests a deeper study on the density of spm.
The scale deposit has two different aspects, one is the crystal
structure (Matyskin et al., 2017), the other is an amorphous layer
formed at a lower strata. This last can be made of asphaltenic com-
pounds or made of amorphous iron oxides. As expected, all the evidence
points out that barite is the main compound associated to radioactivity,
and in this case the formed crystals are homogeneous. However, the
nuclear track contour maps show high and low track density regions,
indicating that the material is not homogeneous at millimeter scale,
since individual crystals are spread over the sample surface showing
empty areas.
In the radiation doses calculation, the total dose (internal and ex-
ternal) limit for occupational standards is assumed to be 20 mSv per
year; while limits applicable to the general public are just 1 mSv per
year. The dust permissible exposure limit (PEL) used was 5 mg m−3,
which considers the usual natural particle distribution as given by the
EPA (EPA/625/R-96/010). However, in order to assess the resulting
radiation dose for workers involved in the handling and recycling of
TENORM rich tubes, it is necessary to evaluate the AMAD and then
make a proper characterization of the radioactivity concentration of the
samples, particularly of the fine grain fractions (the air transportable
ones). In the view of the present results, a study using gamma
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Journal of Environmental Radioactivity 192 (2018) 342–348
Fig. 7. Alpha track density contour map showing the iso-
values. Area is 13 × 15 mm2. Colors indicate track density
along the contours; white/pink hues are in the range of 280-
250 tracks per unit area while yellow hues indicate lower
ranges between 70 and 110 tracks. (For interpretation of the
references to colour in this figure legend, the reader is re-
ferred to the Web version of this article.)
spectrometry for measuring the radioactivity concentrations is ad-
visable. These dosimetry studies are complex, since the final doses will
depend on the applied safety standard, workers safely protocol and
local environmental conditions (ICRP, 1994).
5. Conclusions
Radioactive incrustations (TENORM) were observed in several off-
line tubes in different oil production pipe storage sites in Venezuela.
Four different types of scales were observed, containing mainly barite,
quartz and calcite. Barite is the compound directly related with the high
radioactivity levels found in the scale samples and it is layered directly
onto the internal tube surface by precipitated dissolved alkaline-earth
salts. It was observed that the plate out mineral samples containing
barite also contained alpha emitters; which confirms the presence of
radium isotopes and its decay products. All the indirect evidence points
to that Ra is present in the crystalline structures of barite as radium
sulfate, as it has been generally suggested. From the electron micro-
scope digitalized images, the barite crystals show low porosity, that
account directly for the radium component; on the other hand its
daughters are in a negligible concentration in those inlays mainly due
radon gas volatility.
Calcite is also produced by precipitation process during water ex-
traction, however, in the present set of samples no trace of radioactivity
was observed. This could be attributed to the low radium content in the
corresponding produced waters, since in the past considerable levels of
radioactivity associated to calcite inlays have been measured. The
presence of quartz was observed which highlights the evidence of
particle dragging processes. Also, remains of hydrocarbons (asphaltenic
compounds) and amorphous iron oxides (from the corroded internal
tubes surfaces) were observed.
Bulk dose rate can be as high as 25 μSv h−1, which exceeds the
occupationally exposed personal dose rate of 10 μSv h−1 derived from
the annual limit of 20 mSv/y (calculation based in 2000 labor hours per
year). However, the inferred high radioactivity concentrations asso-
ciated to natural alpha emitters, as Ra isotopes and its daughters, im-
plies that also the radiological risk of internal exposition must be con-
sidered and evaluated. Special care should be taken with radioactive
barite crystals since they can have a fine grain distribution as reported
above, that increases the risk of inhalation or ingestion. In that context,
it is advisable to apply gamma spectrometry to determine the radio-
activity concentration of the radioactive scales (type A, B and C).
Safety standards and sound management must be designed and
followed in order to reduce exposure to NORM at workplaces.
Therefore, it is conveninet to establish NORM contaminated pipe
handling procedures based on results of this study. Albeit, this work
H. Barros et al.
provides an initial study and highlights some major aspects that are
encountered during oil-extraction, in order to design a general remedial
technique and protocol, a larger set of samples should be conveniently
studied.
Acknowledgements
This study was partially funded by: IAEA through the TCP VEN/7/
012 National Project “NORM/TENORM Monitoring in Industrial by-
products: Radiological and Environmental Protections and uses as building
materials” (2018–2019); PDVSA-INTEVEP; the Universidad Pedagógica
y Tecnológica de Colombia (UPTC), Project SGI-2162. L.S-B acknowl-
edges the financial support from UPTC as visiting professor.
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